Foam crop maturant

ABSTRACT

IT IS DISCLOSED THAT THE MATURITY OF CROP-BEARING CAN BE HASTENED BY TREATMENT OF THE PLANT WITH AN AQUEOUS FOAM HAVING A DISCONTINUOU GAS PHASE COMPRISING CARBON MONOXIDE OR AN UNSATURATED HYDROCARBON HAVING FROM 2 TO ABOUT 4 CARBONS AT A DOSAGE ADEQUATE TO PROVIDE FROM ABOUT 1 TO 300 POUNDS OF THE GASEOUS AGENT PER ACRE. TYPICALLY, THE FOAM COMPOSITION CONTAINS UP TO 10 VOLUMES OF THE GASEOUS AGENT PER VOLUME OF LIQUID AND THE STABILITY OF THE FOAM IS SUFFICIENT TO MAINTAIN THE AGENT IN CONTACT WITH THE PLANT FOR A PERIOD FROM ABOUT 5 TO ABOUT 300 MINUTES, ADEQUATE TO PERMIT THOROUGH ASSIMILATION OF THE GASEOUS AGENT BY THE PLANT AND EFFECT THE HASTENING OF THE MATURITY OF THE TREATED PLANT.

3,810,749- FOAM CROP MATURANT Donald C. Young, Fullerton, Calif., assignor to Union Oil Company of California, Los Angeles, Calif. No Drawing. Filed Nov. 26, 1969, Ser. No. 880,417 I Int. Cl. A01n 5/00, 9/00 US. Cl. 71-70 12 Claims 3,810,749 Patented May 14, 1974 ice.

thecrop ripen or reach harvesting maturity at the same time. Additionally, the efficiency of the mechanical har- 'vesters is improved when the fruit and/or foliage of the plant is more readily severed from the plant as the result of the grOWth'Of abscission tissue. The treatment L of the plant with a gaseous agent is particualrly advanperiod from about 5 to about 300 minutes, adequate to permit thorough assimilation of the gaseousagent by the plant and effect the hastening of the maturity of the treated plant. a

DESCRIPTION OF THE INVENTICN It is known that various gaseous agents such as ethyl- A ene, carbon monoxide, acetylene, etc. hasten the maturity of some plants by inducing or accelerating such growth phenomenonas' flowering (differentiation) of asexual plants, fruit ripening, petiole abscission and foliage necrosis. Of these agents, ethylene is known to exhibit the greatest effect. Practical applications of this knowledge have heretofore been limited because of the failure of prior investigators to develop a practical method to envelop plants in an atmosphere rich in the gaseous agent. Accordingly, practical application of the ripening effect has been limited to treatment of harvested fruit by storing the fruit in an atmosphere containing a gaseous hydrocarbon such as ethylene.'- In vivo uses, by application to plants, has been limited to the use of very large volumes of an aqueous charcoal suspension saturated'with ethylene to*pineapple' to induce differentiation. Someprior investigators have suggested that the plant or-crop could be treated by covering the plant with a plastic tent andintroducing ethylene under the tent. This technique, while useful. for laboratory investigations, has no applicability to commercial or field practice. In fact, this procedure 'isoften impractical even on a laboratory scale since some investigators have performed experiments on excised plant tissue rather than in vivo experiments, thereby incurring the risk that their conclusions'may not be-applicable to growing, unharvested crops. I 1

The failure of the prior techniques to 'developa practical method for the applicationof gaseous agents These mechanical harvesting techniques often destroy the plant and, therefore, require that the majority of tageous in thisregard since such treatment generally hastens both ripening and defoliation. I have now found that crop bearing plants can be treated with an effective amount of a gaseous agent and the agent can be maintained in contact with the plant for sufficient time' to permit itsassimilation into the crop bearingplant by the application, -to the foliage of the plant or surrounding ground, of the agent as a discontinuous gas phase within an aqueous foam formed from water containing the necessary additives to decrease its surface tension and/or increase its viscosity sufiiciently to provide an aqueous foam having a stability from about 0.5 to about 300 minutes or longer.

The-gaseous agent which is used to efiect the aforementioned plant responses can be carbon monoxide-or any volatile unsaturated hydrocarbon, typically those having from 2 to about 4 carbons and includingacetylenic and ethylenic hydrocarbons. Examples of these include ethylene, propylene,-butene, isobutene, acetylene, methylacetylene, dirnethylacetylene, ethylacetylene, etc. Of these, ethylene is the most active and preferred agent. The gaseous agent can be used alone, in admixture with other gaseous agents, or in admixture with a suitable inert diluent gas such as carbon dioxide, air, nitrogen, a saturated hydrocarbon such as ethane, propane, butane, etc. The inert diluent gas can be used as desired, in amounts comprising from 1/10 to 10/1, preferably from 1/5 to 5/1 parts per part of gaseous treating agent, so as to extend the volume of foam from that obtained in the absence of the inert diluent gas. 7 Various surface active agents can be added to achieve thelowered surface tension of the water and various water. soluble polymers and viscous additives can be added to enhance the viscosity of the water and thereby stabilize the foam. Various mechanical techniques can be employed to produce the foam from the aqueous medium. and the hydrocarbon vapor, e.g., a froth can be produced by admixing the aqueous medium and the gaseous agent under high mechanical agitation or, preferably, the gaseous agent can be injected immediately upstream of a. mixing nozzle which discharges the aqueous medium and produces a foam. I

The various surface active agents which can be added to waterto reduce its surface tensions from about dynes per centimeter'to a value of about 15 to about 50 dynes per. centimeter, preferably to about 20 to about 40 dynes per centimeter, can in general be any of the conventional oil-in-water surfactants. The amount of the surface active agent so added can vary from about 0.1 to about 10, preferably from about 0.5 to 5 weight percent, and such surface activation can be of the cationic, anionic or nono s y e. -1

Examples. of the cationic surfactants. include: fatty amines, e.g., dodecylamine, octadecylamine \(Armeens, Duomeens of Armour Chemical Company); alkarylamines, e.g., dodecyl aniline, fatty amides such as fatty imidazolines, e.g., undecylimidazoline prepared by condensing lauric acid with ethylene diamine or oleylaminodiethylamine prepared by condensing the oleic acid with asymmetric diethylene diamine (Sapamine CH by Ciba);

quaternary alkyl and aryl ammonium salts and hydrates,

e.g., cetyltriethyl ammonium cetyl sulfate, dimethylbenzyldodecyl. amrnonium chloride, etc.; quaternary ammonium bases offatty amides of disubstituted diamines, e.g., oleyl methylamino ethylene diethylamine methyl sulfate (Sapamine MS by Ciba), oleylbenzylamino ethylene diethyl- Company.

ainine hydrochloride (Sapamine ECH by Ciba); fatty derivativesofbenzirnidazolines such' as are'prepared by condensation of a fatty acid withorthophenylene-diamine followed by alkylation of the condensate with an alkyl halide to' yield an N-alkyl "alkylbenzimidazole, e.g.,"N-meth-yl N,N'-diethyl heptadecylbenzimidazole; .N-fatty alkyl pyridinium compounds, e.g., laur'yl pyridinium, octadecyl pyri-' dinium "(Fixanol of'Imperial' Chemical Industries)', octadecyl methylene pyridinium acetate, etc. Examples of useful anionic surface active'agents'inelude the following: fatty acid glyceride sulfonates and fatty acid sulfonates, e.g., .sulfonated cottonseed oil, su'la fonated oleic acid, sulfonated sperm oil, sulfonated'tallow, etc.; 'sulfonated fatty amides, e.g., sulfonated amide of ricinoleic acid (Humectol. CA by I. G. 'Farben); sodium salt of sulfuric ester of oleyl diisobutyl amide (Dis'rnulger'i Vof I. G.Farben),'etc.; sulfonated anilidesof fat's, e.g., sodium-salt'of sulfuric ester of oleylethyl anilide (Humectol CX by-I. G. Farben); etc.; amides of aminosulfonic acids, e.g., sodium sulfonate of'oleylmethyl tauride (Ige pon' T by I. G. Farben); amides from condensation of fatty acid chlorides with aminoacids, e.g., 'sodium salt of oleyl sarcoside '(Medialan A by IJG. Farben); sulfdnated aromatic hydrocarbons, e.g., benzene 'sulfonic, naphthalene sulfonic acids and their'ammoniurn and alkali metal salts, etc.; 'alkylaryl sulfonates, e.g., dodecylbenzene sulfonates, octad'ecylbenzene sulfonates, etc.

Illustrative nonionic compounds include the polyethyle'ne oxide condensates with hydrophobic groups having a reactive hydrogen. The hydrophobic group can have from about to 25 carbon atoms and from 2to aboutmolecular weight of ethylene oxide are commonly condensed per molecular weights of hydrophobic group. The hydrophobic group can be selected from a variety of organic compounds having one or more reactive hydrogens including fatty alkyl or alkenyl alcohol, fatty acids,"fatty amines, fatty amide, esterified hexitans or alkyl or 'alkenyl phenols.

As described, the source of the hydrophilic"group,.is ethylene oxide. Other source materials can be employed, for example, ethylene chlorohydrin, or polyethylene-glycol; however, because of its low cost and availability, ethyl- Chemical Company and Priminox 10" of the Rohm and Haas Chemical Company. Y 7

Another class of suitable wetting agents are the reaction products of ethylene oxide with fatty acid partial esters of hexitans. Such compounds are obtained by treating a hexitol, e.g., sorbitol, manitol, dulcitol, etc.; with a dehydrating agent toform the corresponding hexitan, i.e., sorbitan, rnannitan, dulcitan, etc. The hexitan is then partially esterified with a long chain 'fatty acid,'f having between about 8 and about 22 carbon atoms; suclias dodecanoic .acid, pentadecanoic acid, hexadecanoic acid, oleic acid, stearic acid, etc., to replace one of the reactive hydrogens of the hexitan with the'carboxylic radical. The

v i resultant partial ester is then reaoted withethylene oxide.

.Very: suitable emulsifiers comprise the organic substituted ammonium ,salts of sulfodicarboxylic acids that are reacted. with various hydrophobic groups such as fatty amides having 12 to 1 8 carbons to prepare half amides in the manner described in 2,976,209, or with fatty amines having-12 m 26 carbons to prepare half amides in the manner described in 2,976,211, or with polyethoxylated fatty aminesinthe manner described in 3,080,280, or with fattyacid esters of hydroxyl amines to obtain'half amides in;the manner'described in 2,-976, 208.

Various viscous additives can be added to the aqueous medium to increase its viscosity and thereby serve to enhance or stabilize the foam. These 'viscous additives are a class of'water soluble polymers of natural or synthetic origin which are commonly used as protective colloids. .Ihese polymers commonly have molecular weights from 10,000. to 5,000,000 and can be naturally occurring maene oxide is used almost exclusivelyin the p'repar-ationwf phenyl, hexenyl phenol, "hexadecyl phenol,' 1dodecenyl phenols, tetradecyl phenol, heptenyl cresol, isoarnylctsol,

decyl resorcinol, -cetenyl re'sorcinol, isodode'cyYphenol, decenyl xylenol, etc. Examples of commercially available wetting agents belonging to this cl'assand having a-'fatty acid constituent and containing ethylene oxide are thefollowing: Ninosol- 100, Ninosol 200"'and"Nifio'sol 210 of the Alrose Chemical Company and NopaIcDIL-D of the Nopeco Chemical Company. f I A third class of hydrophobic reactants-comprises the alkyl and alkenyl alcohols containing betweenfabout 8 'and about 22 carbon atoms. Among such"alcohol's; are 'dodeca'nol, t'r'idecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, decosenol,'-*etc.'"'A commercially available wetting agent of this typeandfcon taining ethyleneoxide is'Brij 30 of 'The' Atlas Powder such compounds are dodec anamide, tridecylamind-tetra decenamide, pentenyl'amine, hexadecyl'amin' anamide, octadecyl amine, oleic amide, etc.

xamples of terials, e.g., proteins, alginates, cellulose ethers or entirely synthetic polymers, e.g., polyvinyl alcohol, partially hydrolyzedpolyacrylamide, maleic acid or anhydride copolymers polyvinyl pyrrolidone and copolymers thereof, etc. gExamples of proteinaceous materials include the naturally occurring vegetable and animal proteins having molecular .weightsfrom about 34,000 to about 200,000. Examples of such includecasein with a molecular weight of from about 12,000 to 98,000; edestin with a molecular weighnfrom about 29,000 to 200,000; hemoglobin having a" molecular weightfrom about 16,000 to 67,000; egg alburnin having a, molecular weightfrom about 33,000 to 34,000 orserum albumin having a molecular'weight from about 70,000 .to-80,000. Other proteins include glutenin obtained'fromwheat, keratin obtained from animal horn and hoof, etc. Ease of solubility can be attained by partial hydrolysis of the aforementioned proteinaceous materials in' accordance with common practice.

:Them'aleic polymers include copolymers and partially hydrolyzed copolym'ersof maleic anhydride or acid with interpolymei'izable .vinylidene monomers such as vinyl acetate, vinyl methl ether, ethylene, isobutylene or styrene. These polymers .canbe prepared by conventional polymerizationsiand, optionally, can be partially hydrolyzed in an aqueous medium at an elevated pH and temperature commercially available wetting agents in this'group' co n for a few minutes to several hours to promote water'sol- :ubilityrAlso useful are polyvinylpyrrolidone or copoly- Jmers'of vinyl pyrrolidone and interpoly'rnerizable vinylidene monomers such as vinyl methyl ether, vinyl acetate,

.,-. vinyl 'butyl ether, styrene, etc.

J-f/Illustrative ,of commercially available polyvinylpyrrolidone are.type NP,.molecular weight'of 40,000; K-60 "molecularweight-of 150,000 and K-90 molecular weight of-300,000. r

p a, p a H 'rAnother'class' of suitable viscous additives include the ene oxide units are distributed therebetween. Examples of partiallyfhydrolyzed polyacrylamides and copolymers thereof'with' vinyl monomers such as vinyl acetate, methyl methacrylate, ethyl acrylate, methyl vinyl ether, having from 5 to about "percent of the amide groups hydrolyied'tocarboxylic acids and water soluble'salts thereof, e.g., the alkali metal, ammonium and alkaline earth metal salts such as sodium, lithium, calcium, magnesium, etc. The polyacrylamides are obtained by conventional vinyl polymerization using a free radical initiator to produce a high molecular weight polyacrylamide which can be partially hydrolyzed simultaneously with, or subsequent to its polymerization. The hydrolysis of the polymer can be achieved by prolonged exposure of the polymer to elevated pH and temperature conditions, e.g., treatment of an aqueous solution containing from about 2 to about 15 percent of a polyacrylamide with an aqueous solution of sodium bicarbonate, sodium polyphosphate, trisodium orthophosphate, etc., at a pH of about 8 to 12 and a temperature from about 30 to 100 C.-The hydrolysis is performed for a period of from about 2 to about 10 hours and sufiicient to effect hydrolysis of from 5 to 8, preferably from about 12 to about 67 percent of the amide groups to carboxylic acid or the aforementioned soluble carboxylate groups.

Other additives that can be used to increase the viscosity of the material include the water soluble polyvinyl alcohol and partially hydrolyzed polyvinyl acetate or copolymers thereof with vinyl monomers such as allyl alcohol,

' ethyl acrylate, methyl methacrylate, methyl vinyl ether,

butyl ether, etc. The polyvinyl alcohol is obtained by hydrolysis of polyvinyl acetate which, in turn, is obtained by the free radical solution bulk of emulsion polymerization of vinyl acetate using a free radical initiator. The polyvinyl acetate is thereafter hydrolyzed by conventional means, e.g., an aqueous solution of the polymer is maintained at an elevated temperature from 50 to 125 C. for a period of from 15 to about 240 minutes, sufficient to hydrolyze the acetate groups. The resultant polyvinyl alcohol is thereafter recovered from the aqueous medium by conventional means, e.g., spray drying.

Other water soluble materials that can be used to enhance the viscosity of the aqueous medium include various water soluble alginates, e.g., sodium alkinate, potassium alginate, etc., as well as various-cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, etc.

When the viscous additive is used, it is employed in a sufficient concentration to increase the viscosity of water to a level of about 5 to about 200 centipoises measured at "(3., preferably to a viscosity of about 15 to-about 75 centipoises. Of the aforementioned viscous additives, the protenaceous materials are preferred since they exhibit desirable properties up'on drying of the foam by maintaining the cellular integrity of the foam even though the water medium is evaporated from the foam.

The gaseous treating agent, alone or in admixture with 7 an inert gas, and the aqueous medium are mixed in suitable volumetric proportions, e.g., from about 3/1 to 40/ 1, preferably from about 5/1 to about 15/1, and most preferably from about 7/1 to about 12/1, parts gaseous agent per part of liquid volume.

The transpiration of the gaseous agent into the plant can be facilitated and enhanced by inclusion, in the aqueous medium, of various stomata control agents. These stomata control agents include compositions which will stimulate opening of the stomata and thereby facilitate transpiration of the gaseous agent. Such agents include oxalic acid and its alkali metal and ammonium salts, e.g., ammonium oxalate, sodium oxalate, lithium oxalate, potassium oxalate, etc. The oxalate additive can be used at a concentration from about 0.1 to about 10 weight percent of the aqueous medium used in the foam composition, preferably from about 0.5 to about 3 weight percent. Other stomata control agents that can be included comprise the water soluble azides, e.g., the alkali metal and ammonium azides such as sodium azide, potassium azide, lithium acid, ammonium azide, etc., that can be used in concentrations from about 0.01 to about 5.0; preferably from about 0.1 to about 3.0, weight percentof the aqueous medium of the foam composition. The aforementioned azide compound salts tend to inhibit stomata activity and freeze the position of the'stomata. Consequently, the application of the azide containing foam composition to plants at a time when the stomata are mostly open will result in a high transpiration of the gaseous treating agent into the cellular tissue of the plant over an extended period since the azide will inhibit closing of the stomata.

The foam can be applied to the crop-bearing plants or to the ground surrounding the plants using conventional application equipment such as the standard spray rigs employed for the application of liquid pesticides and defoliants now used extensively in agriculture. In addition, the various aerial applicators used for application of pesticides and defoliants can also be used for the application of the liquid foam of this invention. The equipment can be modified for application of the foam of this invention by providing a gas distributor along the length of the spray boom with means to admix the gaseous treating agent and aqueous spray from the spraying rig at a point immediately upstream of the aqueous spray discharge nozzle at each of the nozzle locations along the length of the spray rig. The nozzles can be modified to provide nozzles having a high pressure drop, i.e., a minimal orifice diameter to intimately admix or thoroughly agitate the mixture of aqueous media and gaseous, treating agent as a discharge from the nozzle and thereby form requisite foam containing the gaseous agent as a discontinuous, phase, trapped by the continuous foam phase.

The application of the foam can be varied, depending on the nature of the crop being treated. The foam can be applied directly to the plant foliage and/or the fruit on the plant and this is the preferred treatment with all plants. With crop-bearing trees such as citrus, deciduous fruits and nuts, application of the foam to the foliage or fruit is far superior to application to the soil. With crop- .bearing plants that are small shrubs or vegetables, e.g.,

strawberries, tomatoes, grapes, etc., the foam can also be applied to 'the ground surrounding the plant. In this application, the foam slowly releases the gaseous agent to the atmosphere surrounding the plant over an extended period of from 5 to about 300 minutes or longer. The plant can then adsorb the gaseous agent from the atmosphere which has been enriched in the gaseous agent by slow decomposition of the foam. With all plants, however, it is preferred to avoid the intervening atmosphere transfer of the gaseous treating agent by direct application of the foam to the crop-bearing plant.

The method can be applied to any of the various agricultural crop-bearing plants whenever a ripening, desiccation or defoliation, or differentiation (flowering) effect is desired. Examples of suitable plants with which a ripening effect is desirable and which can be treated with the foam in accordance with this invention include fruit-bearingplants such as pineapple, citrus, e.g., lemon, orange, grapefruit, tangerines, etc., deciduous fruit and nut hearing plants such as apples, cherries, prunes, grapes, peaches, nectarines, pears, plums, prunes, almonds, walnuts, etc. Plants with which a ripening of the fruit and, in addition, a defoliation of the plant foliage is useful include the various stem and fruit vegetables such as rhubarb, celery, cucumbers, tomatoes, peppers, peas, beans, etc. The method can also be applied to effect defoliation of various crop-bearing plants such as the root and tuber vegetables, e.g., sweet potatoes, potatoes, peanuts, sugar beets, etc., or agricultural crops such as cotton, sugar cane, seed crops, e.g., alfalfa, Ledino and red clover, milo, rice, etc.

Incidental to the ripening effect that this treatment can have on the aforementioned fruit-bearing crops, the treatmen in many instances also promotes the growth of the abscission layer on the petiole of the fruit so' that the fruit can be harvested more easily. This is of particular advantage with the various mechanical harvesting means which are finding increasing acceptance in the agricultural industry.

The treatment can also be applied to hasten maturity by. inducing differentiation or flowering of asexual plants. In this application, the foam containing the gaseous treating agent is applied to the plant or to the soil immediately adjacent the plant when the plant is at its incipient flowering state. The treatment is made at dosages sufficient to induce flowering but insufficient to effect defoliation or desiccation. Dosage levels should be from about 0.2 to about pounds of the gaseous treating agent per acre. To some extent, these dosage levels overlap those prescribed for defoliation and desiccation of crop-bearing plants preparatory to harvesting and the different effects of these treatments is partly caused by the different development states of the plant. Thus, young plants at their incipient flowering state are more resistant to defoliation and desiccation than are plants approaching harvesting maturity and treatment of the younger plants with the aforeindicated dosages of the gaseous treating agent can be made without incurring undesired defoliation or desiccation.

Various plants can be treated. In my copending parent application Ser. No. 851,436, there is described a treatment of pineapple. Other crops include strawberries where the treatment to induce flowering can also prevent the subsequent occurrence of albinoism of the fruit, citrus such as oranges, lemons, grapefruit, etc., deciduous fruitbearing plants such as cherries, apples, grapes, etc., tomatoes, peas, cucumbers, etc.

The foam containing the gaseous agent as a discontinuous phase can be applied to the crop-bearing plants shortly prior to harvesting and at a sufficient dosage to provide a concentration of the gaseous agent on or about the plants from about 1 to about pounds gaseous agent per acre, effective to hasten ripening of the crop. The dosage can be varied somewhat depending on the treatment and the size of the crop bearing plant. Thus, the

apple plants bearing fruit of a degree of maturity for an expected harvesting within days. The foam compositions are applied using a portable applicator having a pressure tank of ethylene and a pressure vessel filled with an aqueous solution of 5 weight percent Aerofoam, a commercial foam formula comprising a surfactant and a partially hydrolyzed protein derived from soybean or hoof and horn meal.

The ethylene was used to pressure the liquid vessel. The liquid is discharged through a flow control nozzle and a liquid flow meter into a conventional foaming nozzle. This nozzle, Tee Jet No. ll3DU-DI% has an internal venture nozzle with a 50 mesh screen extending across the venture discharge. The nozzle is modified to connect an 0 ethylene supply line to the gas inlet ports of the venturi the field are adjusted to provide liquid dosages of 50 and 100 gallons per acre in randomized replicate plots. The effect of an added solute, ammonium nitrate, was also investigated by the incorporation of about 7 weight percent ammonium nitrate in the aqueous solution of the foam formula.

The fruit was inspected for ripeness and rated by the Shell Color Rating standard in the industry. This rating is expressed on a scale of 0-5 wherein the following relationships apply.

treatment of tree crops, such as the citrus and deciduous b Degree of lpeness, percen2t fruit and nut trees obviously requires the application of greater quantities of foam than the treatment of vegetable crops. Regardless of the crop treated, it is preferred th 63 87 when the application is made onto the plant that it be at a 4 5 88 I sufficient dosage to cover substantially all of the foliage of 0 the plant. The following table summarizes the results.

TABLE Ripenlng ratingdays after treatment Experiment Ethylene G.p.a/ NH4NO3, Nozzle number liquid dosage percent discharge 7 10 13 15 1 saturated 1, 000 None 1. 2 1. 3 2. 3 2. 7 1 10/1 100 None 1. 5 1. 8 2. 7 a. 1 15/1 100 7.2 1.6 1.8 2.3 3.1 10 1 None 1. 5 1. 7 2. 7 2. 9 15/1 50 None 1. 9 2. 1 3. 1 3.5 20/1 50 None 2. 0 2. 2 a. 2 3. 5 10/1 50 7.2 1.6 1.7 2.6 2.8 15/1 50 7.2 1.7 1.7 2.5 2.8 20/1 50 7.2 1.5 1.7 2.8 3.1 10 1 100 None 1. 7 1. 8 2. 9 3. 3 15/1 100 None 1. 3 1. 4 2. 5 2. 8 10/1 100 7. 2 1. 8 1. 9 2. 9 3. 2 15/1 100 7.2 1.6 1.8 2.8 3.5 10/1 100 7. 2 1. 5 1. 6 2. 7 3. 0 15 1 100 7.2 1.4 1.7 2.7 3.0 10/1 100 None 1.9 1. 9 3. 0 a. 2 15 1 100 None 1. 9 2. 1 3. 0 3. 2 15/1 250 7.2 1.1 1.3 2.1 2.3 15/1 250 7.2 1.3 1.4 2.2 2.4

1 Suspension of 0.2 weight percent charcoal saturated with ethylene. 2 Air, not ethylene, is used as the foaming gas.

EXAMPLE 1 V The compositions are employed for hasteningthe maturity of pineapple (ripening) by their application to pine- The data reveal that all treatments, except the extremely high dosages of experiments 18 and 19, hastened ripening of the fruit to a greater degree than did treatment with the saturated aqueous charcoal suspension (Exp. 1). The presence of the ammonium nitrate retarded this effect only slightly and the application of greater dosages (up to g.p.a.) permitted comparable ripening to that with no ammonium nitrate at the 50 gallon per acre dosage.

EXAMPLE 2 The equipment described in the previous example is used to treat tomato plants bearing green, immature fruit. Before treatment, the plants are inspected and tomatoes of comparable immaturity are tagged. The foam is ap- Plant des- NHINOZ, icca- Fruit percent Nozzle tion ripening,

Experiment:

1 On a scale of 1-10 where represents complete desiccation. i gnta scialg o1-5 where 5 represents complete ripening of all fruit.

n rea e EXAMPLE 3 The equipment described in Example 1 is used to treat pepper plants to desiccate and defoliate the plants and thereby facilitate their harvesting. The ethylene is admixed with the liquid at a volumetric ratio of about 40/1 and the liquid dosage is about 130 gallons per acre. The

following results are obtained.

Plant des- NHtNOa iccation Experiment:

1 None 2 2..- 5.4%(601bs.lacre) d 3 Gneck, no treatment- 2 In experiments on peppers it has been demonstrated that the following desiccation can be expected by the application of ammonium nitrate containing about 1.0 weight percent of an oil-in-water emulsifier.

Plant NHaNOa, desiclbsJacre cation Experiment:

A comparison of the results indicate that the use of the foam containing ethylene as the discontinuous phase enhanced the desiccation to a value equal to that obtainable, in the absence of ethylene, only at twice the dosage of ammonium nitrate.

The preceding data, therefore, evidence that ethylene serves to intensify the desiccation effect of ammonium nitrate.

The specific modes of practice illustrated by preceding examples are intended solely to illustrate application of the invention and to demonstrate results obtainable therewith. It is not intended that these examples be unduly limiting of the invention, but rather that other reagents and plants as well as method steps described herein and their obvious equivalents be included in the scope of the invention.

I claim:

1. A method for facilitating the harvesting of a field of crop-bearing plants that comprises treating, at a time from 5 to about 45 days prior to the expected time of harvesting, said crop-bearing plants with carbon monoxide or an unsaturated hydrocarbon having from 2 to about 4 carbons in an amount effective to hasten the maturity of the crop-bearing plant by application to said plant or to the soil adjacent said plant of an aqueous foam having a discontinuous gas phase comprising carbon monoxide or an unsaturated hydrocarbon having from 2 to about 4 carbons and a continuous aqueous phase with proportions of 3 to about 40 volumes gas phase per volume aqueous phase, said aqueous phase containing an additive selected from the class consisting of surface active agents and a protective colloid comprising a water soluble polymer and mixtures thereof in an amount sufiicient to maintain said foam for a period of from 5 to about 300 minutes.

2. The method of claim 1 wherein said unsaturated hydrocarbon is ethylene.

3. The method of claim 1 wherein said unsaturated hydrocarbon is acetylene.

4. The method of claim 2 wherein said aqueous phase contains a surface active agent sufiicient to decrease the surface tension of the aqueous phase to about 15 to 50 dynes per centimeter.

5. The method of claim 2 wherein said aqueous phase contains a water soluble polymer at a concentartion effective to increase the viscosity of the aqueous phase to about 5 to 200 centipoises.

6. The method of claim 2 as applied to fruit-bearing plants with a sufiicient quantity of said unsaturated hydrocarbon to elfect ripening of said fruit.

7. The method of claim 2 as applied to crop-bearing plants with a sufiicient quantity of said unsaturated hydrocarbon to effect defoliation of the plant.

8. The method of claim 5 wherein said viscosity additive comprises a protein having a molecular weight from 34,000 to 200,000.

9. The method of claim 2 wherein said foam is formed by an admixture of ethylene and an aqueous liquid in proportions of from 5 to 15 parts by volume of ethylene per part by volume of said liquid.

10. The method of claim 1 wherein said gas phase is employed in amounts from 5 to about 15 parts by volume per volume of said liquid.

11. The method of claim 6 wherein plants bearing immature pineapples are treated with said foam to hasten the ripening of said pineapples.

12. The method of claim 6 wherein plants bearing immature tomatoes are treated with said foam to hasten the ripening of said tomatoes.

References Cited UNITED STATES PATENTS 2,242,429 5/1941 Johnson 7l127 3,689,245 9/1972 Weidman et al. 71-67 3,692,512 9/ 1972 Sachnik 71-65 2,245,867 6/1941 Mehrlich 71Dig. l

FOREIGN PATENTS 486,113 5/ 1938 Great Britain 7l-Dig. 1 971,630 9/ 1964 Great Britain 71-Dig. 1

OTHER REFERENCES Chem. Eng. News, Feb. 3, 1969, p. 35.

Sachnik: 22nd Annual So. Weed Sci. Proceedings, 1969, pp. 392-396.

I AMES 0. THOMAS, IR., Primary Examiner U.S. C1. X.R. 71--65, 127, Dig. 1 

